ES2450393T3 - Cationic pyridine and pyridazine dyes - Google Patents

Abstract

Laundry treatment composition comprising: (i) from 2 to 70% by weight of a surfactant, from 0.005 to 2% by weight of a fluorescing agent and from 0.0001 to 0, 1% by weight of a blue or violet cationic pyridine/pyridazine dye of the following structure: **Formula** in which: X is selected from: N; CH; and C-N>=N-phenyl(B)-para-NR1R2; R1 and R2 are independently selected from H, alkyl, aryl; alkylaryl; alkyl esters; polyethers; and R1 and R2 may join to form a five or six membered aliphatic ring which may comprise an additional heteroatom selected from oxygen and nitrogen; R3 is selected from: H; I rent; alkylaryl; and aryl; and, ring A may be further fused with a benzene ring; and An- is a counterion.

Description

Cationic pyridine and pyridazine dyes

5 Field of Invention

The present invention relates to the supply of dyes to fabrics.

Background of the invention

10 Many garments turn yellow after many wash-use cycles, reducing the aesthetic value of the garment. In order to maintain the white appearance, tinting dyes can be used. For main wash applications, these are preferably violet dyes. Normally direct violet dyes, such as direct violet 9 or 99, have been used and these dyes are described in WO 2005014769 and WO 2005003274. Dyes

15 direct accumulate along multiple washes, and this can lead to a strong blue or violet color in the garment. To make this excessive tinting acceptable, a lower level of dye should be used, reducing the benefit.

WO 2007/084729, issued to Proctor and Gamble, discloses the use of thiazolium dyes in 20 formulations for laundry washing as a shading agent that does not accumulate over multiple washes.

WO 2007/087252, issued to Milliken, discloses the use of thiazolium dyes in laundry formulations as a shading agent that does not accumulate over multiple washes.

25 GB 1491930, issued to L'Oreal, discloses cationic pyridine-based mono-azo dyes in a hair dyeing composition.

Summary of the invention

It has been found that the cationic blue and violet N-heterocyclic mono-azo dyes of the present invention provide better performance in laundry applications with respect to those disclosed in WO 2007/084729 and WO 2007/087252 .

In one aspect the present invention provides a laundry laundry treatment composition comprising:

(i) from 2 to 70% by weight of a surfactant, from 0.005 to 2% by weight of a fluorescent agent and from 0.0001 to 0.1% by weight of a pyridine dye / blue or violet cationic pyridazine of the following structure:

in which:

45 X is selected from: N; CH; and C-N = N-phenyl (B) -para-NR1R2;

R1 and R2 are independently selected from H, alkyl, aryl; alkylaryl; alkyl esters; polyethers; and R1 and R2 may be joined to form a five or six membered aliphatic ring that may comprise an additional heteroatom selected from oxygen and nitrogen; R3 is selected from: H; I rent; alkylaryl; and aryl; Y

50 ring A may be further condensed with a benzene ring.

The C-N = N-phenyl (B) -para-NR1R2 group as indicated indicates the ortho substitution of the azo group with respect to quaternary nitrogen in the structure.

In another, the present invention provides a domestic method of treating a textile material, the method comprising the steps of: (i) treating a textile material with an aqueous solution of the cationic pyridine / pyridazine dye, the aqueous solution comprising from 1 ppb to 1 ppm of the cationic pyridine / pyridazine dye, and from 0 ppb to 1 ppm of another dye or pigment selected from: pigments, hydrophobic dyes and direct dyes; and from 0.0 g / l to 3 g / l of a surfactant; (ii) optionally rinse the textile material; and (iii) dry the textile material. Preferably, the aqueous solution comprises 0.1 to 50 ppm of fluorescent agent.

5 Preferably the textile material to be washed is composed of cotton, polyester, nylon or elastane fibers.

Detailed description of the invention

The cationic pyridine / pyridazine dyes as used in the present invention are blue or violet. In this sense, cationic pyridine / pyridazine dyes provide a blue or violet color to a white cloth with a pitch angle of 240 to 345, more preferably 260 to 320, most preferably 270 to 300. The white cloth used It is woven for bleached non-mercerized cotton sheets.

The aromatic rings and R1, R2 and R3 of the dye may be further substituted with suitable non-charged organic groups. Individually suitable non-charged organic groups must have a molecular weight of less than 400, preferably less than 150. The uncharged organic group must contain less than or equal to 3 carbon-carbon double bonds (C = C), most preferably no carbon-carbon double bond.

Preferably, the uncharged organic groups are selected from methyl, ethyl, NHCOCH3, CH3O, C2H5O, HO, amine, Cl, F, Br, I, NO2, CH3SO2, C2H5SO2, CN, CONH2. Preferably, any aromatic ring in the cationic pyridine / pyridazine dye is not directly substituted with OH, that is, a phenolic moiety should not be present.

A polyether (polyether) chain is defined as at least two repeating units that are chemically linked through the oxygen of the ether. The polyether chain can be branched or linear. Preferred polyether chains of ethylene oxides or propylene oxides are selected. When a polyether and / or alkyl chain is present, the chain preferably has a molecular weight of less than 1000, more preferably less than 400, even more preferably less than 200. Preferably R1 and / or R2 is a polyether chain

30 as defined above.

Examples of polyether groups are (CH2CH2O) 4H, (CH2CH2CH2O) 3H, (CH2C (CH3) HO) 3H, (CH2CH2O) 2 (CH2C (CH2O (CH2CH2O) 2H) 2H and those described in WO 2008/087497.

35 An- is a counterion. An is not an essential aspect of the invention and can vary widely. An- can be an anion such as RCOO -, BPh4-, ClO4-, BF4-, PF6-, RSO3-, RSO4-, SO42-, NO3-, F-, Cl-, Br- or I-, where R is hydrogen , optionally substituted alkyl or optionally substituted aryl. Preferably An- is selected from: CH3SO3-, CH3CO2-, BF4-, Cl-, F-, Br- and I-.

When R1 and R2 join to form an aliphatic ring it is preferred that the aliphatic ring be a morpholine or piperidine ring.

The azo group is preferably in ortho with respect to quaternary nitrogen.

When A is further condensed with a benzene ring, ring A forms an extended aromatic ring system of the form:

50 or or

Most preferably, R1 and R2 are selected from: H; polyethers, C1-C8 alkyl which may be substituted with -OH, O-C1-C8 alkyl, -Cl and -F, -CN; -C1-C8-C (O) alkyl 2-C1-C8 alkyl; -C1-C8-OC (O) -C1-C8 alkyl; -C1-C8-alkyl alkyl; -C1-C8-naphthyl alkyl; phenyl; and naphthyl, in which benzyl and phenyl may be substituted with a group

10 selected from: -O-C1-C6 alkyl, -C1-C6 alkyl. More preferably, R1 and R2 are selected from: -H; -CH3; -C2H5; - (CH2) 3H; - (CH2) 4H; -C2H4OH; -C2H4Cl; -C2H4CN; -C6H5; -CH2C6H5; -C2H4OCOCH3; -C2H4COOCH3; and -C2H4OC2H4OH. The most preferred groups for R1 and R2 are methyl or ethyl.

Preferably, R3 is selected from: H, C1-C8 alkyl, -C1-C8 alkyl-phenyl; -C1-C8-naphthyl alkyl; phenyl; and naphthyl.

More preferably, R3 is selected from methyl, ethyl and benzyl. The most preferred groups for R3 are methyl or ethyl.

Ring B can carry up to two groups that are selected from: -Br; -Cl; -F; -NO2; -CN; -SO2-benzyl; -C (O) C1-C8 alkyl; -O-C1-C8 alkyl; -NHC (O) C1-C4 alkyl, -SO2-C1-C8 alkyl; and -SO2-phenyl. More preferably -Br;

20 -Cl; -F; -O-C1-C4 alkyl and -NHC (O) C1-C4 alkyl. When ring B is further substituted it is preferably ortho and / or meta with respect to the amine group -NR1R2. If substituted with 2 groups, one is preferably in ortho and the other in goal with respect to the amine group -NR1R2 and on opposite sides of the ring (ie, in positions 2, 5). The most preferred substituents for ring B are selected from methyl, Cl, NHCOCH3, CH3O and C2H5O.

25 Deposition of the dye on polyester can be increased by increasing the number of hydrophobic organic groups in the dye. Hydrophobic organic groups are groups that increase the calculated logP of the dye compared to an H substituent.

30 Preferred example compounds:

The synthesis of these compounds is well commented in the literature, documents US 3117116 (Hoechst), US

2864813 (Geigy), US 3562245 (Hoechst) and US 3510488 (Kuhlmann).

For inclusion in alkaline detergent powders it is preferred that the dyes be granulated with an acid binder as described in WO 2007/039042 (Unilever). This reduced degradation due to alkaline hydrolysis in storage.

Surfactant

The composition comprises between 2 and 70% by weight of a surfactant, most preferably from 10 to 30% by weight. In general, the nonionic and anionic surfactants of the surfactant system can be chosen from the surfactants described in "Surface Active Agents" vol. 1, from Schwartz & Perry, Interscience 1949, vol. 2 by Schwartz, Perry & Berch, Interscience 1958, in the current edition of "McCutcheon's Emulsifiers and Detergents" published by Manufacturing Confectioners Company or in "Tenside-Taschenbuch", H. Stache, 2nd ed., Carl Hauser Verlag, 1981. Preferably The surfactants used are saturated.

Suitable nonionic detergent compounds that can be used include, in particular, the reaction products of compounds having a hydrophobic group and a reactive hydrogen atom, for example, aliphatic alcohols, acids, amides or alkylphenols with alkylene oxides, especially ethylene oxide either alone or with propylene oxide. Specific non-ionic detergent compounds are condensates of C6 to C22 ethylene alkylphenol oxide, generally 5 to 25 EO, that is 5 to 25 units of ethylene oxide per molecule, and the condensation products of primary or secondary C8 to C18 alcohols , linear or branched, aliphatic with ethylene oxide, generally 5 to 40 EO.

Suitable anionic detergent compounds that can usually be used are metal salts

Water-soluble alkalines of organic sulfates and sulphonates having alkyl radicals containing from about 8 to about 22 carbon atoms, the term "alkyl" being used to include the alkyl part of higher acyl radicals. Examples of suitable synthetic anionic detergent compounds are sodium and potassium alkyl sulfates, especially those obtained by sulfating higher C8 to C18 alcohols, produced for example from tallow or coconut oil, sodium and potassium C9 to C20 alkylbenzenesulfonates, particularly C10 to alkylbenzenesulfonates C15 linear secondary sodium; and sodium alkyl glyceryl ether sulfates, especially the ethers of the higher alcohols derived from tallow or coconut oil and synthetic petroleum-derived alcohols. Preferred anionic detergent compounds are C11 to C15 alkyl sodium benzenesulfonates and C12 to C18 sodium alkyl sulfates. Surfactants such as those described in EP-A-328177 (Unilever), which show resistance to salt precipitation, the surfactants of

Alkyl polyglycoside described in EP-A-070074 and alkylmonoglycosides.

Preferred surfactant systems are mixtures of active materials of anionic and non-ionic detergent, in particular the groups and examples of anionic and non-ionic surfactants indicated in EP-A-346 995 (Unilever). Especially preferred is the surfactant system which is a mixture of an alkali metal salt of a C16 to C18 primary alcohol sulfate together with a 3 to 7 EO ethoxylate of C12 to C15 primary alcohol.

The non-ionic detergent is preferably present in amounts greater than 10%, for example 25 to 90% by weight of the surfactant system. Anionic surfactants may be present, for example, in amounts in the range of from about 5% to about 40% by weight of the surfactant system.

In another aspect that is also preferred, the surfactant can be a cationic one so that the formulation is a tissue conditioner.

Cationic compound

When the present invention is used as a tissue conditioner it needs to contain a cationic compound.

Most preferred are quaternary ammonium compounds.

It is advantageous if the quaternary ammonium compound is a quaternary ammonium compound having at least one C12 to C22 alkyl chain.

It is preferred that the quaternary ammonium compound have the following formula:

wherein R1 is a C12 to C22 alkyl or alkenyl chain; R2, R3 and R4 are independently selected from

C1 to C4 alkyl chains and X- is a compatible anion. A preferred compound of this type is the quaternary ammonium compound quaternary cetyltrimethylammonium bromide.

A second class of materials for use with the present invention are the quaternary ammoniums of the above structure in which R1 and R2 are independently selected from C12 to C22 alkyl or alkenyl chain; R3 and R4 are independently selected from C1 to C4 alkyl chains and X- is a compatible anion.

A detergent composition according to claim 1 wherein the ratio of (ii) cationic material with respect to

(iv) anionic surfactant is at least 2: 1.

Other suitable quaternary ammonium compounds are disclosed in EP 0 239 910 (Proctor and Gamble).

It is preferred that the ratio of cationic surfactant to non-ionic is from 1: 100 to 50:50, more preferably 1:50 to 20:50.

The cationic compound may be present at from 1.5% by weight to 50% by weight of the total weight of the composition. Preferably the cationic compound may be present at from 2% by weight to 25% by weight, a more preferred composition range is from 5% by weight to 20% by weight.

The softening material is preferably present in an amount of from 2 to 60% by weight of the total composition, more preferably from 2 to 40%, most preferably from 3 to 30% by weight.

The composition optionally comprises a silicone.

Detergency builders or complexing agents:

Detergency adjuvant materials may be selected from 1) calcium sequestrant materials, 2) precipitation materials, 3) calcium ion exchange materials and 4) mixtures thereof.

Examples of detergent adjuvant materials calcium sequestrants include alkali metal polyphosphates, such as sodium tripolyphosphate and organic sequestrants, such as ethylenediaminetetraacetic acid.

Examples of adjuvant precipitation detergency materials include sodium orthophosphate and sodium carbonate. Preferably, the laundry laundry treatment composition comprises sodium carbonate in the range of from 5 to 50% by weight, most preferably from 10 to 35% by weight.

In the method, when used with a treatment composition for granular laundry, the aqueous wash solution preferably comprises 0.1 to 4 g / l sodium carbonate.

Examples of calcium ion exchange detergency adjuvant materials include the various types of water-insoluble crystalline or amorphous aluminosilicates, of which zeolites are the best known representatives, for example zeolite A, zeolite B (also known as zeolite P) , zeolite C, zeolite X, zeolite Y y

45 also the type P zeolite as described in EP-A-0.384.070.

The composition may also contain 0-65% of a detergency adjuvant or complexing agent such as ethylenediaminetetraacetic acid, diethylenetriamine-pentaacetic acid, alkyl or alkenyl succinic acid, nitrilotriacetic acid or the other detergency adjuvants mentioned below. Many detergency builders are also bleaching stabilizing agents by virtue of their ability to complex metal ions.

Zeolite and carbonate (including bicarbonate and sesquicarbonate) are preferred detergency builders.

The composition may contain as a detergency adjuvant a crystalline aluminosilicate, preferably an alkali metal aluminosilicate, more preferably a sodium aluminosilicate. Normally this is present at a level of less than 15% by weight. Aluminosilicates are materials that have the general formula:

0.8-1.5 M2O.Al2O3.0.8-6 SiO2

wherein M is a monovalent cation, preferably sodium. These materials contain some bound water and are required to have a calcium ion exchange capacity of at least 50 mg of CaO / g. Preferred sodium aluminosilicates contain 1.5-3.5 SiO2 units in the above formula. They can be easily prepared by the reaction between sodium silicate and sodium aluminate, as widely described in the

65 bibliography. The ratio of surfactants to aluminosilicate (when present) is preferably greater than 5: 2, more preferably greater than 3: 1.

Alternatively or additionally to aluminosilicate detergency builders, phosphate builder builders can be used. In this technique the term "phosphate" encompasses species of diphosphate, triphosphate and phosphonate. Other forms of detergency adjuvant include silicates, such as soluble silicates, metasilicates, silicates

5 stratified (for example SKS-6 from Hoechst).

Preferably the laundry detergent formulation is a laundry detergent formulation without phosphate builder, that is, contains less than 1% phosphate by weight.

Enzymes

The composition may comprise one or more enzymes, which provide cleaning performance, tissue care and / or hygiene benefits.

15 Fluorescent Agent

The composition preferably comprises a fluorescent agent (optical brightener). Fluorescent agents are well known and many such fluorescent agents are commercially available. Typically, these fluorescent agents are supplied and used in the form of their alkali metal salts, for example, sodium salts. The total amount of the fluorescent agent or agents used in the composition is generally from 0.005 to 2% by weight, more preferably from 0.01 to 0.1% by weight. Preferred classes of fluorescent agent are: di-styrylbiphenyl compounds, for example Tinopal (trademark) CBS-X, di-amine-stilbenedi-sulfonic acid compounds, for example Tinopal DMS pure Xtra and Blankophor (trademark) HRH, and compounds of pyrazoline, for example Blankophor SN. Preferred fluorescent agents are: 2- (4-styryl-3

Sulfophenyl) -2H-naphthol [1,2-d] sodium triazole, 4,4'-bis {[(4-anilino-6- (N-methyl-N-2-hydroxyethyl) amino-1,3, 5-triazin-2il)] amino} stilbene-2-2'-disulfonate disodium, 4,4'-bis {[(4-anilino-6-morpholino-1,3,5-triazin-2-yl)] disodium amino} stilbene-2-2 disulfonate and disodium 4,4'-bis (2-sulfoestyryl) biphenyl.

Fragrance

Preferably the composition comprises a perfume. The perfume is preferably in the range of from 0.001 to 3% by weight, most preferably from 0.1 to 1% by weight. Many examples of suitable perfumes are provided in the 1992 International Buyers Guide of the CTFA (Association of Cosmetics, Toiletries and Fragrances), published by CFTA Publications and OPD 1993

35 Chemicals Buyers Directory, OPD of 1993, 80th annual edition, published by Schnell Publishing Co.

It is common for a plurality of perfume components to be present in a formulation. In the compositions of the present invention it is anticipated that there will be four or more, preferably five or more, more preferably six or more or even seven or more different perfume components.

In perfume mixtures, preferably 15 to 25% by weight are output notes. The output notes are defined by Poucher (Journal of the Society of Cosmetic Chemists 6 (2): 80 [1955]). Preferred output notes of citrus oils, linalool, linalyl acetate, lavender, dihydromyrcenol, rose oxide and cis-3-hexanol are selected.

The perfume and the head note can be used to give rise to the whiteness benefit of the invention.

It is preferred that the laundry laundry treatment composition does not contain a peroxygen bleach, for example, sodium percarbonate, sodium perborate and peracid.

Polymers

The composition may comprise one or more polymers. Examples are carboxymethyl cellulose, poly (ethylene glycol), polyvinyl alcohol, polycarboxylates such as polyacrylates, maleic / acrylic acid copolymers and copolymers

55 lauryl methacrylate / acrylic acid.

Polymers present to prevent dye deposition, for example polyvinylpyrrolidone, poly (vinylpyridine N-oxide) and polyvinylimidazole, are preferably absent in the formulation.

Experimental part

Example 1

SYNTHESIS OF IODIDE 1,5-DIMETHYL-2 - [(4-DIMETHYLAMINE) -PHENYLAZO] -PIRIDINIO 65

(i) Preparation of dispersed dye, 5-methyl-2 - [(4-dimethylamino) -phenylazo] -pyridine. 2-amino-5-picoline (2.16 were added

g) and sodamide (50% w / w suspension in toluene, 1.56 g) to toluene (60 ml) and the mixture was heated to reflux for 30 min. 4-Nitroso-N, N-dimethylaniline (3 g, 0.02 m) was added in small portions (exothermic reaction) and refluxing was continued under argon for 3 hours. After cooling, the mixture was evaporated to dryness under reduced pressure to leave a tar residue that was extracted with hot acetic acid (2 x 100 ml). The yield of the remaining reddish brown insoluble material was 2.3 g. The acetic acid extracts were neutralized by carefully adding sodium hydroxide liquid (40%) to pH 7: this resulted in a color change, from violet to brown, and the precipitated tar solid was collected. This was washed with water several times, by decantation, and the remaining solid was extracted with methylene chloride. The combined methylene chloride extracts were dried, the solvent was removed and the residue was chromatographed on silica gel. He

The desired product was a dark red crystalline solid (0.57 g, 12%), m.p. 152-154 ° C.

(ii) Preparation of 1,5-dimethyl-2 - [(4-dimethylamino) -phenylazo] -pyridinium iodide. 5-Methyl-2 - [(4-dimethylamino) phenylazo] -pyridine (0.7 g) was added to methylene chloride (25 ml), followed by iodomethane (11.4 g), and the mixture was heated to reflux for 8 hours Ethyl acetate (30 ml) was added and methylene chloride and the distillate were distilled off.

15 residual iodomethane. Upon cooling, a crystalline solid was collected, washed with additional ethyl acetate (30 ml) and dried.

Yield 1.4 g, m.p. 210-213 ° C.

20 Example 2

SYNTHESIS OF IODIDE 1-METHYL-2 - [(4-DIMETHYLAMINE) -PHENYLAZO] -CHINOLINUM

(i) Preparation of the dispersed dye 2 - [(4-dimethylamino) -phenylazo] -quinoline.

The scale (0.02 m) and method used were similar to those used for the preparation of 5-methyl-2 - [(4-dimethylamino) -phenylazo] -pyridine, but replacing 2-aminopyridine with 2-aminoquinoline (2 , 88 g, 0.02 m). In addition, the toluene suspension of 2-aminoquinoline and sodamide was allowed to cool before adding 4-nitrosoN, N-dimethylaniline (3 g, 0.02 m). After removal of toluene, the residual tar was stirred with methylene chloride and

30 was passed through silica gel. The eluate was collected, the solvent was removed and the residue was treated with ispropanol to provide a brown solid, m.p. 149-151 ° C.

(ii) Preparation of 1-methyl-2 - [(4-dimethylamino) -phenylazo] -quinolinium iodide. 2 - [(4-dimethylamino) were heated

phenylazo] -quinoline (1.1 g, 0.004 m) and iodomethane (11.4 g, 0.08 m) in methylene chloride (20 ml) at reflux for 35 18 h. The mixture was allowed to cool and a solid product, a greenish violet microcrystalline solid, was collected.

Yield 1.65 g, 85%, m.p. 223-225 ° C.

Example 3

40 UV-Vis spectra were recorded in buffered water up to pH = 7 of the dyes. The spectra were recorded in a 1 cm cell with an optical density of 1.

Lambda dye max / nm

Example 4

The dyes listed below were added to a washing powder so that when 4 g / l dissolved

5 of the powder in water, the optical density at the lambda max. of the dye in the range 400-700 nm was 1 to 5 cm. In this way the same amount of color was added to each powder. The wash powder contained 20% LAS surfactant, 30% Na2CO3, 40% NaCl, the remaining minor compounds included calcite and fluorescent agent and moisture. The washing powder was used to wash a 1: 1: 1 mixture of white woven cotton fabric, white polyester fabric and white nylon-elastane fabric. This simulates the types of mixed fabrics found in loads of

10 domestic washing. Washings were carried out in hard water with 26º French hardness at 293 K with a washing liquid ratio with respect to 30: 1 cloth. The washings lasted 30 minutes and were followed by 2 rinses of 1 minute in hard water with 26º French hardness at 293 K. After washing the tissues were dried and their color was measured using a reflectometer (excluding UV) and the color was expressed as CIE values L * a * b *. DE values (compared to the dye-free wash control) were calculated from this.

The experiment was repeated using wash water at 333 K and rinse water at 293 K.

The table below shows the LE values obtained in the cotton experiment.

Dye LE 293 K LE 333 K

14.3 15.0

23.3 13.8

11.6 13.3 7.3 9.5

6.9 10.5

Comparative example 9.8 10.2

Basic Violet 35 is a cationic thiazole monoazoic dye Comparative example

5.1 5.6 Basic blue 159 is a mono -zoic dye of 3,5-thiadiazole, cationic

Comparative example

The dyes of the present invention provided more color to the fabric as indicated by its higher values of 5 LE.

Powder formulations of base A, B, C and D by way of example

Formulation

TO B C D

Nalas

14 twenty 8 14

NI (7EO)

- - - 10

Na tripolyphosphate

- fifteen - -

Na Alkylsulfate

2 - 2 -

Soap

- - - 2

Zeolite A24

7 - - 17

Sodium silicate

5 4 5 one

Sodium carbonate

25 twenty 30 twenty

Sodium sulfate

40 33 40 22

Carboxymethyl cellulose

0.2 0.3 - 0.5

Sodium chloride

- - - 5

Lipase

0.005 0.01 - 0.005

Protease

0.005 0.01 - 0.005

Amylase

0.001 0.003 - -

Cellulase

- 0.003 - -

Pyridine / cationic pyridazine dye

0.0015 0.002 0.002 0.003

Fluorescent Agent

0.1 0.15 0.05 0.3

Water / impurities / minor components

Rest Rest Rest Rest

The powder formulations A, B, C and D were prepared with the three pyridine / pyridazine of Example 3 at the indicated level. eleven

Liquid formulations of base A, B, C and D by way of example

Formulation

TO B C D

Nalas

14 10 fifteen twenty-one

NI (7EO)

10 5 twenty-one fifteen

SLES (3EO)

 7 10 7 -

Soap

2 4 one 0

Citric acid

one one - one

Na Alkylsulfate

- - 0.5 2

Glycerol

0 one 5 0

Propylene glycol

5 3 0 4

Sodium chloride

one - - -

Ethoxylated amine polymers

0.5 one - -

Triethanolamine

0 0.5 3 one

Fragrance

0.2 0.1 0.3 0.4

Protease

0.005 0.01 - 0.005

Amylase

0.001 0.003 - -

Lipase

- 0.003 - -

Fluorescent Agent

0.1 0.15 0.05 0.3

Pyridine / cationic pyridazine dye

0.002 0.003 0.0008 0.004

Water / impurities / minor components

Rest Rest Rest Rest

5 Powder formulations A, B, C and D were prepared with the three pyridine / pyridazine of Example 3 at the indicated level.

For both powder and liquid formulations, enzyme levels are given as a percentage of pure enzyme. NI (7EO) refers to R- (OCH2CH2) nOH, in which R is a C12 to C15 alkyl chain and n is 7. NaLAS is linear alkylbenzenesulfonate (LAS) and (SLES (3EO)) is polyethoxylate sulfate (3 , 0) C12-C18 alkyl. Alkylsulfate

10 Na is PAS.

A three rinse conditioner formulation was also created, for use in the rinse stage of the wash. It contained 13.7% by weight of N, N-di (seboyloxyethyl) -N, N-dimethylammonium chloride, 1.5% by weight of perfume, 0.001% by weight of the three pyridine / pyridazine of Example 3 , remaining minority compounds and water.

Claims (9)

1. Composition of treatment for washing clothes comprising: (i) from 2 to 70% by weight of a surfactant, from 0.005 to 2% by weight of a fluorescent agent and from 0.0001 to 0.1% by weight of a pyridine dye / blue or violet cationic pyridazine of the following structure: 10 in which: X is selected from: N; CH; and C-N = N-phenyl (B) -para-NR1R2; R1 and R2 are independently selected from H, alkyl, aryl; alkylaryl; alkyl esters; polyethers; and R1 and R2 may be joined to form a five or six membered aliphatic ring that may comprise an additional heteroatom selected from oxygen and nitrogen; R3 is selected from: H; I rent; alkylaryl; and aryl; Y, The ring A may be further condensed with a benzene ring; and An - is a counterion. 2. A laundry detergent composition according to claim 1, wherein the azo group is ortho with respect to quaternary nitrogen. 25 3. A laundry detergent composition according to claim 1 or 2, wherein R1 and R2 are selected from: H; polyethers, C1-C8 alkyl which may be substituted with -OH, O-C1-C8 alkyl, -Cl, and -F, -CN; -C1-C8C (O) alkyl 2-C1-C8 alkyl; -C1-C8-OC (O) alkyl-C1-C8 alkyl; -C1-C8 alkyl-phenyl; -C1-C8-naphthyl alkyl; phenyl; and naphthyl, in which benzyl and phenyl may be substituted with a group selected from: -O-C1-C6 alkyl, -C1 alkyl  30 C6. 4. A laundry detergent composition according to any preceding claim, wherein R3 is selected from: H, C1-C8 alkyl, -C1-C8 alkyl-phenyl; -C1-C8-naphthyl alkyl; phenyl; and naphthyl. 5. A laundry detergent composition according to any preceding claim, wherein ring B carries up to two groups that are selected from: -Br; -Cl; -F; -NO2; -CN; -SO2-benzyl; -C (O) O-C1-C8 alkyl; -O-C1-C8 alkyl; -NHC (O) C1-C4 alkyl, -SO2-C1-C8 alkyl; and -SO2-phenyl. 6. A laundry detergent composition according to claim 3, wherein R1 and R2 are selected from:  40 -H; -CH3; -C2H5; - (CH2) 3H; - (CH2) 4H; -C2H4OH; -C2H4Cl; -C2H4CN; -C6H5; -CH2C6H5; -C2H4OCOCH3; -C2H4COOCH3; and -C2H4OC2H4OH. 7. A laundry detergent composition according to claim 6, wherein R1 and R2 are selected from: methyl and ethyl. Four. Five

8.

 Composition of laundry detergent according to claim 4, wherein R3 is selected from methyl, ethyl and benzyl.

9.

 Composition of laundry detergent according to any preceding claim, wherein the agent which

50 fluoresce is selected from the group consisting of: 2- (4-styryl-3-sulfophenyl) -2H-naphthol [1,2-d] triazole sodium, 4,4'bis {[(4-anilino-6- (N-methyl-N-2-hydroxyethyl) amino-1,3,5-triazin-2-yl)] amino} stilbene-2-2'-disulfonate disodium, 4,4'bis {[(4-anilino -6-morpholino-1,3,5-triazin-2-yl)] amino} -stylbeno-2-2'-disulfonate disodium and 4,4'-bis (2-sulphostyryl) biphenyl disodium. 10. A domestic method of treating a textile material, the method comprising the steps of: (i) treating a textile material with an aqueous solution of the cationic pyridine / pyridazine dye as defined according to any one of claims 1 to 8 , comprising the aqueous solution from 1 ppb to 1 ppm of the cationic pyridine / pyridazine dye, and from 0 ppb to 1 ppm of another dye or pigment selected from: pigments, hydrophobic dyes and direct dyes; 5 and from 0.0 g / l to 3 g / l of a surfactant; (ii) optionally rinse the textile material; Y 10 (iii) dry the textile material. 11. A domestic method of treating a textile material according to claim 10, wherein the aqueous solution comprises 0.1 to 50 ppm of the fluorescent agent.